Lubricating composition, a wax depressor therefor, and its method of preparation



Patented Jan. 9 1945 UNITED STATES PATENT OFFICE- LUBRICATING COMPOSITION, A,WAX DE- PRESSOR THEREFOR, AND ITS METHOD OF PREPARATION Eugene Licber, Staten Island, N. Y., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing.-

Application December 28, Serial No. 372,195

18 Claims. (01. 252- 52) This invention relates to a novel type of chemical condensation product and to methods of pre-' paring such products and using them for various purposes, more particularly as pour depressors in waxy lubricating oils.

One object of the present invention is to make wax modifiers especially useful as pour depressors in waxy lubricating oils from raw materials not heretofore known to be capable of being converted into pour depressors, namely, the class of alkylated phenols containing short chained alkyl groups, i. e., less than 6 carbon atoms.

It is already known that pour depressors can be made by various condensation reactions involving the use of long chained aliphatic compounds, as for example, the condensation of chlorinated paraffin wax with naphthalene; and

it is also known that pour depressors can be made by acylation of alkylated phenols having long chained alkyl groups such as those derived from paraffin wax. However, it has generally been considered necessary by those skilled in the art when making pour depressors to always use at least one reactant having long chained aliphatic groups, and it was also usually considered desirable to have a plurality of such long chained aliphatic groups present for each aromatic molecule present. However, by means of the present invention a way has been discovered for obviat-' ing the necessity of either of those two factors,

around the aromatic nucleus in respect to the hydroxyl group and that the alkyl groups may be straight chained or branched. Also, there can be two or more hydroxy groups and there can be two or more alkyl groups present, although the results are generally at least as good with only a single alkyl group, if not better, as compared with two or more alkyl groups. I

Instead of the naphthalene nucleus other polynuclear aromatic compounds may be used, such as suitable alkylated and hydroxy derivatives of anthracene, phenanthrene, diphenyl, etc.

Although there are some alkylated phenols on the market, i. e., commercial products, such as tertiary amyl phenol, which are suitable for use according to the present invention, it is possible to start with an unalkylated phenol. and treat it with a low molecular weight alkyl halide or an namely, the long chained aliphatic groups and, r

the use of a plurality of such groups.

Broadly, this invention comprises the production of wax-modifying agents by chemically con- I densing an aliphatic-substituted hydroxy arc-- matic compound containing aliphatic 'groups having only less than 6 carbon atoms and containing as little as only one such group, with an acylating agent.

The aliphatic-substituted hydroxy aromatic compound to be used should preferably'have the general formula RnAI'-OH, in which R represents an aliphatic group, preferably analkyl group,

having less than 6 carbon atoms, n is 1 to 4, preferably 1 to 2, and Ar is an aromatic nucleus.

The phenols and naphthols containing low molecular weight aliphatic substituents are typical members of this class of compounds. Some specific examples include the various amyl phe nols such as para-tertiary amyl phenol, isobutyl phenol, n-butyl phenol, isopropyl phenol, n-

' propyl phenol, cresols, etc., as well as mono-amyl, alphaor beta-naphthol, butyl naphthols, propyl,

naphthols, etc. It should be understood that the alkyl groups can be located in various positions olefin in the presence of a Friedel-Crafts type catalyst, such as aluminum chloride, in order to make the alkylated phenol, as for instance, by reacting ordinary phenol with amyl chloride in the presence of aluminum chloride to produce para-amyl phenol. The resulting reaction mass containing the amyl phenol can be used directly for the present invention without isolating the amyl phenol itself. This can be done merely by adding the dibasic acid as acylating agent, and, if necessary, by adding an additional quantity of catalyst;

The acylating agent to be used according to the present invention should be organic dibasic acid and may either have the general formula (CHzhKCOOHlz where n equals 0 to 30, preferably 2 to 10, or may have the general formula Ar(CO0H)2, where Ar represents an aromatic nucleus such as the nucleus 06114, in phthalic acid or phthalic anhydride. The acylating agent is'preferably used in the form of the acid halide or the acid anhydride. Specific examples of suitable acylating agents are the acid chlorides or acid anhydrides of the following acids: oxalic, r'nalonic, succinic, glutaric, adipic, pimelic, su-

beric, and sebacic. 1

To effect the condensation of .the alkylated hydroxy aromatic compound containing low molecular weight alkyl groups, with the acylating agent, according to the present invention, it is preferable to use a. Friedel Crafts catalyst, particularly aluminum chloride, although other'Friedel- Crafts catalysts may be used, such as boron fluoride, zinc chloride, ferric chloride, titanium tetrachloride, boron trichloride and in some cases even anhydrous hydrogen fluoride.

The condensation is preferably carried out in 4 2,808,785 the presence-ofinert solvents, such as a highly refined naphtha or kerosene, tetrachlor-ethane,

- carbon disulfide, etcz, although if desired the use of the solvent may be dispensed with.

The proportions in which the reactions should ora linear type chain up of different types of aromatic nuclei, one type of which was derived 1 from the alkylated hydroxy aromatic compounds be used should usually be about as to mols,

stituted hydroxy aromaticcompound to 1 mol ofthe diba'sic acid acylating agent. The amount of catalyst to be used should usually be about 0.2 to 3.0 mols, preferably 0.5 to 2.0 mols per mol of acylating agent. If a solvent is used, the volume thereof should usually be about to 10, preferably 1 to 5, times the total volume of the reactants to catalyst.

In; carrying out the invention, the reaction" temperature should be maintained between the approximate limits of room temperature and about 400 F., preferably between about 100 and" 300 F. The preferred procedure is to add the catalyst to the reactants gradually at room temperature, and then to-heat the reaction mass to the desired maximum temperature, maintain it there, such as by refluxing it for the desired length of time, which would normally be between about 10 minutes and 10 hours, preferably about hour to 5 hours. The temperature and time should be adjusted to give the maximum yield of pour depressor having the desired pour-depressing potency. After the reaction has been completed, the

reaction mixture is cooled and preferably diluted with an inert diluent, such as a refined kerosene, 'then the catalyst is hydrolyzed and neutralized by any of the known methods, such as byrusing a mixture of water and alcohol, or an aqueous ..solution of caustic soda, or even plain water or The whole mass is then allowed plain alcohol. to settle and theaqueous catalyst layer is drawn oil. The upper or kerosene layer containing the desired condensation product dissolved therein, is then subjected to distillation, preferably under low partial pressure as by theusual vacuum, or by distillation with fire and steam, up to a table temperature such as about 600 F. The condensation proddct of this invention is soluble in mineral lubricating oils and has a fairly high molecular weight, as it is substantially non-volatile at temperatures below about 600 F. It'usually has a color" ranging from a green to a brown and has a physical. consistencynr texture ranging from a viscous oil "preferably 1 to 5 mols, of the aliphatic-sub- I and the other of which was derived from an aromaticdibasic acid. In any case, however, the linear chain type structure also possesses some free aliphatic groups which originated as subf stitu'ents 9n the hydroxy aromatic compounds bricating oil having a relatively high pour point,

the resultant blend will have a substantially lower pour point; in other words, this wax' modifler is an effective pour depressor for waxy oil. A small amount of this wax modifier is also useful as a dewaxingaid for removing wax from mineral lubricating oils of undesirably high wax,

, content. In similarly small-amounts, this wax to a resin, in some cases having an intermediate gummy consistency.

' Although the chemical'structure ofthe products of this invention has not been determined with certainty, it is believed that they may be represented by a linear-chained structure having alternate aromatic nuclei, in case the acylating agent used was an aliphatic dibasic acid, 0

modifier may also be incorporated into paraffin wax or compositions containing the same to be used for various purposes such as for coating or impregnating paper, etc. or for making various molded products.

For the sake of illustration, but without limiting the invention to the particular materials used, the following experiment ata are given:

34 grams of 'sebacic acid were treated with 2d grams of phosphorous trichloride on the water bath. The resulting sebacyl chloride was decanted from the phosphorous acid into a solution comprising grams 'of tert-amyl-phenol dissolved in 200 cc. of tetrachlorethane used as solvent. 55 grams of anhydrous AlCh were then slowly added to the reaction mixture. After the addition of the AlCla, the reaction mixture was refluxed under a return condenser for 30 minutes. At the end of this time thereaction mixture-was cooled, diluted with kerosene, and the AlCla destroyed by the addition of water. After settling,'the kerosene extract was distilled with fire and steamto 600 F., in order to remove solvent and low-boiling products. A bottoms residue comprising 64 grams of a brown viscous gummy substance was obtained as product. When2% of my condensation product was added to a waxy oil, the. pour point of which was +30 F., the pour point was found to be 5 F.- A number of other tests were made using more scribed above, except that several different alylated phenols tions of both reactants, and the reaction time. .was varied. The results of all these tests are summarized in the following table. 1

- Table Alkylatedphenol gygg r w- Solvent Product Test A i i Tmp Pour No, L y I F. hmint Name lGm. Name Gm. Name Cc. 2% Appearance blend,

1 T.-am l hcnol. 120 Sebacic acids 34 55 CaHaCh. 200 Reflux" 64 -5 Bro 2 '80 a4 55 200 do as i .-10 3 Di-amyl phenol. 94 do 40 64 do 200 do 3, 127 -20 Green vise. oil. 4 do.. .p. 47 .do l0 54 do 200. o '3 50 -l0 Dark brown resin. 4 k n V l Blend in a waxy iubricating oii base stock haves-pour point of +30 were used and various propor-' or less the same general procedure as that de- It is noted that in all four of the above tests the condensation product produced a 35 to 50 F. lowering of the original pour .point (+30 F.) of a waxy lubricating oil base stock, when added thereto a concentration of 2%. These results are quite remarkable and unexpected, in view of the fact that the prior art has considered that it is practically a necessity to use long aliphatic hydrocarbon chains, and preferably a plurality of same, in making condensation products for use as pour 'depressors.

It is not intended that this invention be limited to any of the specific examples which were givenmerely for the sake of illustration nor to any theory as to the mechanism of the operation of the invention, but only by the appended claims in which it is intended to claim all novelty inherent in the invention as broadly as the prior art permits.

I claim:

1. A wax modifier consisting essentially of a condensation product of a compoundhaving the general formula RnAT-OH, in which'R is an I alkyl group having lessthan 6 carbon atoms, 11.

7 equals 1 to 4 and Ar is an aromatic nucleus, with a dibasic acid having the general formula (CHQMCOOHM, in which n equals 0 to 30, said condensation product being substantially nonvolatile below about 600 F. I

2. A wax modifier consisting essentially of a condensation product of a compound having the general formula R-Ar-OH, in which R is an alkyl group having less than 6 carbon atoms and Ar is an aromatic nucleus, with an acylating agent selected from the group consisting of acid halides and acid anhydrides of a dibasic acid having the general formula (CH2)n(COOH)2, in

which n equals 2 to 10, said condensation prodnot being Substantially non-volatile at temperatures below about 600 F.

3. A wax modifier consisting essentially of a condensation product of an alkylated phenol having less than 6 aliphatic carbon atoms with an acylating agent derived from a dibasic acid hav ing the general formula (CH2)11(COOH)2, in which n equals 2 to 10, said condensation prodless than 6 carbon atoms, with an acylating agent corresponding to the general formula (CH2)n(C OOH)2, in which n equals 0 to 30, and recovering from the condensation product an oilsoluble fraction substantially non-volatile at temperatures below about 600 F.

8. The process which comprises condensing a compoundhaving the general formula RnAl"-OH, in which R is an alkyl group, n equals 1 to 2, and Ar i an aromatic nucleus, with an acylating agent derived from a dibasic acid having the general formula (CHQMCOOH) 2, in which n equals 2 to 10; in the presence of a Friedel-Crafts catalyst, and subjecting the condensation product to distillation at low partial pressure to obtain a distillation residue soluble in hydrocarbon oil, substantially non-volatile at temperatures below R-Ar-OH inwhich R is an alkyl group having less than 6 carbon atoms and Ar is an aromatic nucleus with an aliphatic dibasic. acid acylating agent uct being ubstantially non-volatile at temperatures below about 600 F. and being soluble in hydrocarbon oils.

4. A wax modifier consisting essentially of the condensation product of amyl phenol with an acylating agent derived from dibasic acid having the general formula (CH2)(COOH) z, in which n equals 2 to 10, said condensation prodnot being substantially non-volatile at tempera tures below about 600 F. and being soluble in,

hydrocarbon oils.

5. A wax modifier consisting essentially of an oil-soluble condensation product of a compound having the general formula'RnAr-0H, in which R is anialkyl group having less than 6 carbon atoms, 11. equals 1 to 4, and Ar is an aromatic nucleuswith a sebacic acid acylating agent, said condensation product being substantially nonvolatile at temperatures below about 600 F. a

6. A wax modifier consisting essentially of a Friedel-Crafts condensation product of para-- tertiary amyl phenol withsebacic acid chloride, said condensation product being soluble in hydrocarbon oils and substantially non-volatile at temperatures below about 600 F.

'7. The process which comprises condensing an aliphatic-substituted hydroxy aromatic compound having aliphatic groups containing only having 2 to 10 carbon atoms, in the presence of aluminum chloride as catalyst, 'hydrolyzing and .removing the catalyst and subjecting the condensation product to distillation with fire and steam to about 600 F. to obtain adistillation residue which is soluble in hydrocarbon oils and having wax-modifyin properties. i

10. Process according to claim 9 in which an alkylated phenol is used which contains less than 6 aliphatic carbon atoms.

11. The process of preparing .wax modifiers which comprises condensing .an amyl phenol with sebacicacid chloride in the presence of aluminum chloride at a temperature between the approximate limits of room temperature and about 400 and in the presence of an inert solvent, to produce a high molecular weight condensation product, hydrolyzing and removing the aluminum chloride catalyst and subjecting the condensation product to distillation with fire and a steam to about 600 F.

'12. The process of preparing wax modifiers which comprises condensing about 1 to 5 mols of an alkylated phenol having less than 6 carbon atoms with about 1 mol of an aliphatic dibasic equal to about to 10 times the total volume of reactants and catalyst, at a temperature between the approximate limits of room temperature and about 400 F. for a reaction time sufficient to produce an oil-soluble high molecular weight condensation product havin wax-modifying properties, cooling and diluting the condensation mass with a substantial volume of inert diluent,

hydrolyzing and removing the catalyst and-subjecting the condensation product to distillation with fire and steam to about 600 F. to obtain as distillation residue a condensation prodluct fraction having wax-modifying properties.

13. A composition comprising a hydrocarbon wax and a condensation product of an aliphaticsubstituted hydroxy aromatic compound containing aliphatic groups having only less than 6 carbon atoms, with a dibasic acid acylating agent corresponding to the general formula (CI-1:)(COOHh,

in which n equals 0 to 30, said condensation prodaliphatic dibasic oil and a small amount uct being substantially non-volatile at temperaures below about 600 F. I 14. A composition comprising a wax-containg hydrocarbon oil and, associated therewith, a

wax-modifier consisting essentially of a condensation product of a compound having the general formula RnArOH, in which R' is an aliphatic group having less than 6 carbon atoms, n equals 1 to 2, and Aris an aromatic nucleus, with an acid acylating agent having from 2 to 10 carbon atoms, said condensation product being substantially non-volatile, at temperatures below about 600 F:

15. A lubricating oil composition comprising a major proportion of a waxy mineral lubricating of a wax modifier consisting essentially of a condensation'product of a.

compound having the general formula R-Ar-OH l in which R is an alkyl group having less than 6 carbon atoms, and 'Ar is an aromatic nucleus,

with an aliphatic dibasic acid acylating agent having from 2 to 10 carbonatoms, said condensa- 7 major proportion of a tion product being substantially non-volatile at temperatures below about 600 F.

16. A lubricating oil composition comprising a major proportion of a waxy mineral lubricating oil and a pour-depressing amount of a condensation. product of an alkylated phenolL-havinglesa than 6 aliphatic carbon atoms with an aliphatic dibasic acid acylating agent having from 2 to 10 carbo atoms, said condensation product being substantially non-volatile attemperatures below "about 600 F.

17. A lubricating oil composition comprising a 011 and'a pour-depressing amount of acondensation product of an am-yl phenol with sebacic acid chloride. 1 Q -i 18. Product according'to claim 1 derived from a compound having the general formula RnAt-OH v an alkyl group having less than 6 nequals 1 to2, andArisanaro- EUGENE LIEBER.

in which R is carbon atoms, matic nucleus.

waxy mineral lubricating 

